US20140039794A1 - Evaluating Hydrologic Reservoir Constraint in Coal Seams and Shale Formations - Google Patents

Evaluating Hydrologic Reservoir Constraint in Coal Seams and Shale Formations Download PDF

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US20140039794A1
US20140039794A1 US14/046,953 US201214046953A US2014039794A1 US 20140039794 A1 US20140039794 A1 US 20140039794A1 US 201214046953 A US201214046953 A US 201214046953A US 2014039794 A1 US2014039794 A1 US 2014039794A1
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unconventional
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John Pope
Daniel Buttry
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Gas Sensing Tech Corp
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28Investigating the spectrum
    • G01J3/44Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01VGEOPHYSICS; GRAVITATIONAL MEASUREMENTS; DETECTING MASSES OR OBJECTS; TAGS
    • G01V9/00Prospecting or detecting by methods not provided for in groups G01V1/00 - G01V8/00
    • G01V9/007Prospecting or detecting by methods not provided for in groups G01V1/00 - G01V8/00 by detecting gases or particles representative of underground layers at or near the surface
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B49/00Testing the nature of borehole walls; Formation testing; Methods or apparatus for obtaining samples of soil or well fluids, specially adapted to earth drilling or wells
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering

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  • This disclosure provides a sensing method that evaluates levels of hydrologic constraint in aquifers occurring in unconventional reservoirs, such as shale formations and coal formations. Specifically, the disclosed sensing method measures levels of naturally-occurring 13 C in a reservoir and compares the level of 13 C to the levels typical for highly constrained and highly unconstrained reservoirs. The disclosed sensing method also monitors levels of naturally-occurring 13 C in a reservoir while operations that may unintentionally or intentionally change the constraint in a reservoir are undertaken. Such operations can include, for example, cementing of casing in a wellbore intersecting more than one reservoir, hydraulic fracturing of a reservoir, and horizontal drilling in a reservoir.
  • Isotopic analysis of reservoir fluids in coal seams is a method to evaluate the type of chemical process producing coal bed methane gas retrieved from those seams (Dudley D. Rice, George E. Claypool, AAPG Bulletin, Volume 65, Issue 1. (January), Pages 5-25 (1981)).
  • This method is possible because methanogenic consortia that digest the coal to produce methane preferentially digest moieties containing 12 C atoms. Thus, gases produced by methanogens are enriched in 12 C.
  • hydrologic constraint refers to the extent to which the fluids resident in a coal seam or shale formation are residual from the methanogenic process.
  • highly constrained reservoirs have little or no influx of foreign fluids that are not residual from the methanogenic process.
  • Highly unconstrained reservoirs have appreciable, and sometimes significant, influx of foreign fluids that are not residual from the methanogenic process.
  • Such foreign fluids can include, but are not limited to, fluids from other geological formations, fluids from surface waters, fluids from recharge at formation outcrop, and others. Influx of such fluids can occur by a variety of mechanisms including, but not limited to, via a wellbore connecting multiple formations, via a multi-formation geological fault, and via fracture networks connected to similar cross formation flow pathways.
  • Coal is the result of coalification, which pertains to the degree of biogenic and then thermogenic transformation of organic sediments. Coalification occurs initially via methanogens. Methanogens perform methanogenesis, a type of biogenic process, which results in enrichment of 13 C isotope because 12 C is consumed as it is easier to metabolize. Thermogenesis however, does not affect 13 C levels to a significant extent. Moreover, surface water generally has non-enriched 13 C levels. Gases produced by thermogenic processes, on the other hand, undergo no such kinetic preferential metabolysis and therefore are not significantly enriched in 12 C. As a result, measurement of 12 C levels in methane gas produced from coals can indicate whether the coal is undergoing biogenic or thermogenic coalification.
  • the natural abundance of 12 C isotopes is about 98.9% of carbon atoms.
  • the natural abundance of 13 C isotope is about 1.1%.
  • the dissolved inorganic carbon (DIC) consists of carbon dioxide/carbonic acids [CO 2 +H 2 CO 3 ], bicarbonate [HCO 3 ⁇ ] and carbonate [CO 3 2 ⁇ ]. Therefore, the tracer of interest is ⁇ 13 C DIC , which is defined as the 13 C/ 12 C ratio in the sample divided by the standard 13 C/ 12 C ratio, minus one, and typically expressed in parts per thousand by then multiplying the result by one thousand.
  • bacteria ferment acetate (CH 3 COOH ⁇ CH 4 +CO 2 ) and reduce carbon dioxide (CO 2 +4H 2 ⁇ CH 4 +2H 2 O).
  • CO 2 +4H 2 ⁇ CH 4 +2H 2 O carbon dioxide
  • bacterial methanogenesis preferentially removes 12 C and the remaining DIC is enriched in 13 C.
  • a positive ⁇ 13 C DIC identifies groundwater in which biogenic production of methane has occurred.
  • the ⁇ 13 C DIC of groundwater that is not associated with methanogenesis have ratios of negative 5% to negative 20%, whereas water coproduced with coal bed methane has ratios as high as +35%.
  • the present disclosure provides a method for determining hydrologic constraints in unconventional reservoirs, comprising:
  • the unconventional reservoirs are coal bed reservoirs and shale fluid reservoirs.
  • the operations in the target unconventional reservoir are selected from the group consisting of cementing of casing in a wellbore intersecting more than one reservoir, hydraulic fracturing of a reservoir, horizontal drilling in a reservoir, and combinations thereof.
  • the present disclosure further provides a method for determining hydrologic constraints in unconventional reservoirs, comprising:
  • the unconventional reservoirs are coal bed reservoirs or shale fluid reservoirs.
  • a difference in respective levels of 13 C between the typical and the target reservoirs is used to predict future production success or failure of the target reservoir.
  • the levels of 13 C are determined by use of Raman spectroscopy.
  • the operations in the target unconventional reservoir are selected from the group consisting of cementing of casing in a wellbore intersecting more than one reservoir, hydraulic fracturing of a reservoir, horizontal drilling in a reservoir, and combinations thereof. More preferably, the levels of 13 C are compared to the levels of levels of 12 C in order to produce a ⁇ 13 C enrichment level.
  • the present disclosure further provides a method for determining hydrologic constraints in unconventional reservoirs, comprising:
  • the present disclosure also provides a method for determining extent of hydraulic fracturing of a target unconventional reservoir, comprising:
  • the unconventional reservoirs are coal bed reservoirs or shale fluid reservoirs.
  • a difference in respective levels of 13 C in the target reservoir before and after fracturing is used to predict future production success or failure of the target reservoir.
  • the levels of 13 C are determined by use of Raman spectroscopy.
  • the levels of 13 C are compared to the levels of levels of 12 C in order to produce a ⁇ 13 C enrichment level.
  • FIG. 1 shows representative Raman spectra of the bicarbonate ion containing (A) 12 C and (B) 13 C atoms dissolved in water.
  • FIG. 2 shows a representative log of ⁇ 13 C enrichment in naturally occurring bicarbonate ions dissolved in reservoir fluid, as measured downhole using a Raman spectrometer in a coalbed methane well.
  • FIG. 3 shows a representative graph of ⁇ 13 C enrichment for reservoir fluids produced from a coal seam before and after hydraulic fracturing was completed on the coal seam.
  • the decrease in ⁇ 13 C enrichment after hydraulic fracturing indicated that the induced fractures connected to one or more adjoining fluid reservoirs, thereby reducing the coal seam's hydraulic constraint, increasing the fluid volumes necessary to be produced in order to produce gas from the coal seam, and injecting hydraulic fracturing fluids and chemicals into the adjoining fluid reservoir or reservoirs.
  • FIG. 4 graphs positive ⁇ 13 C DIC measurement in produced waters from various coalbed reservoirs, showing particularly highly enriched 13 C quantities in fields A and B of 4 fields (A through D).
  • FIG. 5 graphs gas production from 4 fields over 2.5 years.
  • FIG. 6 graphs the water gas ratio of 4 fields (A through D) as a function of ⁇ 13 C DIC .
  • coals contain 13 C enriched fluids.
  • the level of ⁇ 13 C enrichment is a characteristic of each zone and field.
  • surface and non-coal aquifers do not have 13 C enriched aqueous fluids. Therefore, measuring 13 C levels confirms if an aqueous fluid comes from a coal bed. Further, any measured decrease in ⁇ 13 C enrichment from a baseline measurement is thus directly proportional to an influx of aqueous fluid from non-coal zones.
  • the disclosed method is novel and has not been employed during commercial exploration and production of coal bed methane and shale gas.
  • the present disclosure provides a new reservoir evaluation technology that allows operators to high grade prospective shale and coalbed gas properties and target pay zones, allowing operators to avoid non-economic completion costs and water use.
  • This disclosure enables more complete evaluation of shale and coalbed gas resources. This evaluation focuses operators on developing completion methods for shale and coalbed gas targets that warrant investment, reduce overall water usage, and increase the conversion of shale and coalbed gas resources into shale and coalbed gas reserves.
  • the disclosed method removes uncertainty regarding possible fluid influx into reservoirs via recharge or invasion, incenting more rapid capital investment by shale and coalbed gas operators and investors, and accelerating natural gas production from these reservoirs.
  • the disclosed method enables shale and coalbed gas operators to increase exploration success rates, reduce finding costs, reduce completion costs, and reduce environmental impacts without constraining production.
  • Disclosed herein is a method of using an optical spectrometer to measure in situ the relative levels of 12 C and 13 C in fluids produced from coals and shales.
  • This method involves measuring the fundamental vibrational frequencies for molecular bonds and moieties in carbon containing salts.
  • vibrational frequencies depend on the weight of the atoms participating in the vibrational moments.
  • the fundamental vibrational frequencies of 12 C containing molecular bonds occur at higher energies than the fundamental vibrational frequencies of 13 C containing molecular bonds and moieties.
  • optical spectroscopies including but not limited to Raman spectroscopy, infrared spectroscopy, and near-infrared spectroscopy, measure the fundamental vibrational frequencies, or combinations of fundamental vibrational frequencies, in molecules.
  • the shift in vibrational frequency between 12 C and 13 C is approximately proportional to the vibrational shift expected for a spring connecting two masses, where one mass is increased in mass from 12 mass units to 13 mass units.
  • the reduction in vibrational frequency for a molecule containing 13 C is about 1.8% or about 20 wavenumbers. Representative spectra of both 12 C and 13 C containing bicarbonate ion dissolved in water are shown in FIG. 1 .
  • a Raman spectrometer capable of resolving the 12 C and 13 C peaks, and detecting accurately changes in the relative sizes of those peaks, can be used to measure the relative ⁇ 13 C enrichment in coal seam and shale gas reservoir fluids.
  • Raman spectroscopy has been successfully adapted for use in coal seam and shale gas wells, as set forth in previously incorporated U.S. Pat. No. 6,678,050 to Pope et al. Therefore, this invention discloses for the first time the use of Raman spectrometers to measure 13 C enrichment levels in situ, downhole, in coal seam and shale gas wells.
  • Raman spectroscopy has been successfully adapted for use in analyzing at the wellhead fluids produced from coal seam and shale gas reservoirs. See pending application entitled In-Situ Detection And Analysis Of Methane In Coal Bed Methane Formations With Spectrometers, Ser. No. 61/602,939, filed Feb. 24, 2012 which is incorporated in its entirety by reference herein. Therefore, this invention discloses for the first time the use of Raman spectrometers to measure ⁇ 13 C enrichment levels in situ, at the wellhead, in coal seam and shale gas fluid discharge streams.
  • a Raman spectrometer suitable for use in a well is obtained using previously disclosed inventions.
  • One such Raman spectrometer is the device used by the assignee, which is an epi-illuminated, grating equipped Raman spectrometer with a 532 nm laser excitation and charge-coupled device (CCD) detector packaged into a 3-inch diameter, 80 inch long high pressure steel housing.
  • the spectrometer interrogates the surrounding gases or fluids via a one-inch sapphire window located at bottom of its housing.
  • the spectrometer communicates to a surface computer and power unit via a standard four-conductor wireline.
  • the Raman spectrometer wireline tool top sub is connected to a cable head that is connected to a four-conductor wireline spool of appropriate length.
  • the spectrometer is powered up by connecting a power supply to two of the four wires in the wireline.
  • the surface computer communicates with and controls the spectrometer via the other two wires.
  • the spectrometer is operated at the wellhead in order to check its operation and calibration. It is then lowered into the well while Raman spectra are collected at 10 second intervals and then transmitted to the surface computer over a subsequent 20 seconds. When the spectrometer encounters reservoir fluid in the wellbore, the Raman spectrum characteristic of that fluid is measured and transmitted to the surface computer.
  • the human operator reviews that spectrum for quality and character to confirm its origin, and the computer processes that spectrum for spectral features of interest, such as position of peaks and number of photons comprising one or more particular peaks.
  • the Raman spectrometer measures one position and number of photons comprising a 12 C-related bicarbonate vibrational mode and a different position and number of photons comprising a peak corresponding to the 13 C-related bicarbonate vibrational mode.
  • the human operator and/or the computer then evaluate the positions and number of photons for each peak and relate them to each other and/or to a calibration scale measured under controlled laboratory conditions. In this manner, the amount of ⁇ 13 C enrichment in a reservoir fluid is quickly and conveniently measured in a wellbore.
  • a five inch diameter steel casing was completed into a twelve-foot thick coal seam by perforation of the casing.
  • the coal seam was located at 890 feet below surface to 902 feet below surface. Perforations were made from 892 feet below surface to 900 feet below surface. The perforations were performed with 50 feet of water cushion above the perforating gun.
  • the coal seam subsequently flowed 340 feet of additional fluid into the wellbore, so that the wellbore contained 390 feet of fluid total above the mean depth of the coal seam.
  • the top of the fluid column was therefore located at 506 feet below surface.
  • a three-inch diameter, 80 inch long wireline Raman spectrometer tool was subsequently lowered into the wellbore while it was continuously collecting Raman spectra.
  • the Raman spectrometer When it encountered fluid in the wellbore, the Raman spectrometer subsequently collected and transmitted Raman spectra of that fluid (primarily water) and of the analytes in that fluid (primarily methane and bicarbonate containing both 12 C and 13 C isotopes). The spectra were then processed by the computer according to algorithms well known to those skilled in the art of vibrational spectroscopy to produce the concentrations of each bicarbonate isotope at each measured depth. Those concentrations were then mathematically compared to produce a 30% average ⁇ 13 C enrichment in the dissolved bicarbonate present at each depth in the fluid column, as shown in FIG. 2 .
  • the self consistent character of the resulting data at 556 feet below surface reflects the fact that the wellbore contained reservoir fluid at depths greater than 556 feet below surface. This fact was corroborated by examination of the methane concentration and total dissolved solids measured concurrently throughout the fluid column. Based on this result, the coal seam in which that well was completed was judged to be highly constrained. Since the methane gas content measured for the coal seam was of economic quantities, and since the drawdown required to produce gas from the coal seam was measured to be only 145 psia, the coal seam was judged to be an attractive production target.
  • Similar measurements can be undertaken using a variety of fluid handling techniques.
  • the example analysis described above could also be undertaken for multiple coal seams intersected by a cased and cemented wellbore where the casing is perforated sequentially starting with the deepest coal and fluid from each zone is isolated in the casing using an bridge plug, inflation packer, or similar device and Raman spectroscopy testing of ⁇ 13 C enrichment is subsequently undertaken on each isolated fluid.
  • example analysis described above could also be undertaken for multiple coal seams intersected by a cased and cemented wellbore where the casing is perforated in all zones and then the fluid from each zone is isolated and produced using a drill stem testing string, straddle packer, or similar device and Raman spectroscopy testing of ⁇ 13 C enrichment is subsequently undertaken on each isolated fluid.
  • example analysis described above could also be undertaken for multiple coal seams intersected by an uncased wellbore where each seam is isolated and fluid from each seam is produced using a drill stem testing string, straddle packer, or similar device and Raman spectroscopy testing of ⁇ 13 C enrichment is subsequently undertaken on each isolated fluid.
  • the example analysis described above could also be undertaken wherein the Raman spectroscopy testing of ⁇ 13 C enrichment is performed using a Raman spectrometer located at the wellhead that is connected to a fiber optic assembly that is subsequently lowered into the wellbore to contact the fluid. The Raman spectroscopy analysis is then undertaken using the fiber optic assembly to deliver the excitation radiation and collect the scattered photons.
  • This invention discloses for the first time the use of ⁇ 13 C enrichment data to assess whether drilling and completion operations create new flow channels for fluids between the target coal or shale zone and other zones near a wellbore.
  • this invention describes a method of testing an untreated coal or shale zone in order to establish its naturally characteristic ⁇ 13 C enrichment level, treating the coal or shale zone, retesting the coal or shale zone to evaluate whether the treatment created new fluid flow channels to other zones, and then using that information to determine whether the coal or shale zone is an appropriate production target. That information can also be used to determine whether the treatment resulted in contamination to the surrounding zones. That information can also be used to refine the treatment itself in order to reduce or eliminate said contamination.
  • a five inch diameter steel casing was completed into a twelve-foot thick coal seam by perforation of the casing.
  • the coal seam was located at 890 feet below surface to 902 feet below surface. Perforations were made from 892 feet below surface to 900 feet below surface. The perforations were performed with 50 feet of water cushion above the perforating gun.
  • the coal seam subsequently flowed 340 feet of additional fluid into the wellbore, so that the wellbore contained 390 feet of fluid total above the mean depth of the coal seam.
  • the top of the fluid column was therefore located at 506 feet below surface.
  • a three-inch diameter, 80 inch long wireline Raman spectrometer tool was subsequently lowered into the wellbore while it was continuously collecting Raman spectra.
  • the Raman spectrometer When it encountered fluid in the wellbore, the Raman spectrometer subsequently collected and transmitted Raman spectra of that fluid (primarily water) and of the analytes in that fluid (primarily methane and bicarbonate containing both 12 C and 13 C isotopes). The spectra were then processed by the computer according to algorithms well known to those skilled in the art of vibrational spectroscopy to produce the concentrations of each bicarbonate isotope at each measured depth. Those concentrations were then mathematically compared to produce a 30% average ⁇ 13 C enrichment in the dissolved bicarbonate present at each depth in the fluid column, as shown in FIG. 2 .
  • the self consistent character of the resulting data at 556 feet below surface reflects the fact that the wellbore contained reservoir fluid at depths greater than 556 feet below surface. This fact was corroborated by examination of the methane concentration and total dissolved solids measured concurrently throughout the fluid column. Based on this result, the coal seam in which that well was completed was judged to be highly constrained. Since the methane gas content measured for the coal seam was of economic quantities, and since the drawdown required to produce gas from the coal seam was measured to be only 145 psia, the coal seam was judged to be an attractive production target. Hydraulic fracturing of the coal seam was undertaken in order to increase its effective permeability in order to increase its water and gas flow rates.
  • FIG. 3 shows a graph of the ⁇ 13 C DIC in fluids collected from the coal seam before and after hydraulic fracturing. Because the post-frac fluid ⁇ 13 C DIC was reduced substantially from the pre-frac ⁇ 13 C DIC level, it was concluded that the hydraulic fracturing process fractured through the coal seam and into an overlaying limestone.
  • water produced with CBNG are Na-HCO 3 -type water with relatively high TDS (>1000 mg/L) and positive ⁇ 13 C DIC .
  • Water samples from wells with low water/gas ratios have the highest ⁇ 13 C DIC and produce the most gas.
  • Water samples from wells with lower, although still positive, ⁇ 13 C DIC values reflect the addition of isotopically light water from other reservoirs.
  • Structure contour mapping identifies faults in proximity to low ⁇ 13 C DIC wells. Geochemical analysis of ⁇ 13 C DIC help to identify CBNG and shale natural gas reservoirs with the highest potential for natural gas production while minimizing unnecessary water production.
  • ⁇ 13 C DIC should be less enriched in coal bed reservoirs that are hydraulically connected to multiple water sources with isotopically light carbon compositions.
  • An unconfined coal bed reservoir is likely to produce more water during CBNG production than a confined coal bed reservoir, as the hydraulic pressure of multiple connected reservoirs would need to be reduced to promote CBNG desorption.
  • ⁇ 13 C DIC may help producers determine in which geographic areas coal bed reservoir water has undergone the most biologic methanogenic activity and/or those coal bed reservoirs that are confined.
  • Enrichment of ⁇ 13 C DIC is directly related to bacterial methanogenesis.
  • the generation of thermogenic gas will not enrich DIC ratios, and ⁇ 13 C DIC characterization is inapplicable in CBNG reservoirs that are exclusively thermogenic.
  • the ⁇ 13 C DIC alone cannot identify which specific isotopically light reservoirs are in communication with coal bed reservoirs. Water quality, well log, and geologic interpretation of likely reservoirs may aid in distinguishing these reservoirs.
  • a ⁇ 13 C DIC measurement can characterize CBNG reservoirs. Moreover, carbon isotopic tracers in produced water can guide CBNG development to those areas where natural gas production is maximized and water production is minimized. Positive ⁇ 13 C DIC of CBNG produced water indicates that bacterial methanogenesis is associated with these waters ( FIG. 4 ). However, a significant range in ⁇ 13 C DIC exists in Field A CBNG samples, which provides additional information about the potential for CBNG production from individual wells and related reservoirs ( FIG. 5 ).
  • ⁇ 13 C DIC measurements can analyze CBNG production potential, particularly in hydraulically confined CBNG reservoirs. This capability alone makes ⁇ 13 C DIC a significant coal bed reservoir and CBNG analysis tool (FIG. 6 ).
  • a correlation is predicted between water/gas ratios, production potential, efficiency, and ⁇ 13 C DIC , as: (a) ⁇ 13 C DIC should be less enriched in coal bed reservoirs that are hydraulically connected to multiple water sources with isotopically light carbon compositions. (b) An unconfined coal bed reservoir is likely to produce more water during CBNG production than a confined coal bed reservoir, as the hydraulic pressure of multiple connected reservoirs would need to be reduced to promote CBNG desorption.
  • ⁇ 13 C DIC Enrichment of ⁇ 13 C DIC is directly related to bacterial methanogenesis. The generation of thermogenic gas will not enrich DIC ratios, and ⁇ 13 C DIC characterization is inapplicable in CBNG reservoirs that are exclusively thermogenic. ⁇ 13 C DIC alone cannot identify which specific isotopically light reservoirs are in communication with coal bed reservoirs. Water quality, strontium isotopic compositions, well log, and geologic interpretation of likely reservoirs may aid in distinguishing these reservoirs. ⁇ 13 C DIC analysis records the characteristics of the produced water at the time the wells were sampled.

Abstract

Methods and apparatus suitable for quickly and accurately measuring 13C levels and supporting data in an aqueous fluid reservoir. Interpreting the resulting data to indicate key factors regarding a reservoir and completion methods, including reservoir constraint, gas producibility, and completion success. A sensor and to a sensing method that evaluates the level of hydrologic constraint in aquifers occurring in unconventional reservoirs, such as shales and coals is disclosed. Specifically, Raman spectroscopy is disclosed as a sensor and a sensing method that measures the level of naturally-occurring 13C in an aqueous reservoir and compares the level of 13C to the levels typical for highly constrained and highly unconstrained reservoirs. The disclosed sensor and sensing method also monitors the level of naturally-occurring 13C in a reservoir. Also disclosed is a method of using δ13CDic to evaluate geographic areas of coal bed reservoir water having biologic methanogenic activity.

Description

    RELATED APPLICATIONS
  • This application claims priority to U.S. Provisional Application Ser. No. 61/472,623 entitled “Evaluating Hydrologic Reservoir Constraint in Coal Seams and Shale Formations” filed Apr. 7, 2011, the contents of the application which is hereby incorporated herein by reference in its entirety.
  • TECHNICAL FIELD
  • This disclosure provides a sensing method that evaluates levels of hydrologic constraint in aquifers occurring in unconventional reservoirs, such as shale formations and coal formations. Specifically, the disclosed sensing method measures levels of naturally-occurring 13C in a reservoir and compares the level of 13C to the levels typical for highly constrained and highly unconstrained reservoirs. The disclosed sensing method also monitors levels of naturally-occurring 13C in a reservoir while operations that may unintentionally or intentionally change the constraint in a reservoir are undertaken. Such operations can include, for example, cementing of casing in a wellbore intersecting more than one reservoir, hydraulic fracturing of a reservoir, and horizontal drilling in a reservoir.
  • BACKGROUND
  • Isotopic analysis of reservoir fluids in coal seams is a method to evaluate the type of chemical process producing coal bed methane gas retrieved from those seams (Dudley D. Rice, George E. Claypool, AAPG Bulletin, Volume 65, Issue 1. (January), Pages 5-25 (1981)). This method is possible because methanogenic consortia that digest the coal to produce methane preferentially digest moieties containing 12C atoms. Thus, gases produced by methanogens are enriched in 12C.
  • The preferential metabolysis of 12C from coals or shales during biogenesis results in enrichment of 13C in the carbon containing salts and other materials residual to the process. This enrichment has been used to typecast fluids from particular coal seams (Enhancing Microbial Gas From Unconventional Reservoirs: Geochemical And Microbiological Characterization Of Methane-Rich Fractured Black Shales, FINAL REPORT (March 2004-September 2004) Prepared by: Anna M. Martini, Klaus Nüsslein, Steven T. Petsch, Prepared for: RESEARCH PARTNERSHIP TO SECURE ENERGY FOR AMERICA, Subcontract No. R-520) and even to track the eventual impact of the fluids on the environment (http://faculty.gg.uwyo.edu/cfrost/pdfs/2010%20Frost%20CBNG%20book.pdf). But the enrichment of 13C in the carbon containing salts and other materials residual to the preferential metabolysis of 12C from coals or shales during biogenesis has not been used in the manner of the present disclosure, that is, to measure hydrologic constraint. These measurements are made while operations may be undertaken that unintentionally or intentionally change the constraint in a reservoir. More specifically, “hydrologic constraint” refers to the extent to which the fluids resident in a coal seam or shale formation are residual from the methanogenic process. Thus, highly constrained reservoirs have little or no influx of foreign fluids that are not residual from the methanogenic process. Highly unconstrained reservoirs have appreciable, and sometimes significant, influx of foreign fluids that are not residual from the methanogenic process. Such foreign fluids can include, but are not limited to, fluids from other geological formations, fluids from surface waters, fluids from recharge at formation outcrop, and others. Influx of such fluids can occur by a variety of mechanisms including, but not limited to, via a wellbore connecting multiple formations, via a multi-formation geological fault, and via fracture networks connected to similar cross formation flow pathways.
  • Coal is the result of coalification, which pertains to the degree of biogenic and then thermogenic transformation of organic sediments. Coalification occurs initially via methanogens. Methanogens perform methanogenesis, a type of biogenic process, which results in enrichment of 13C isotope because 12C is consumed as it is easier to metabolize. Thermogenesis however, does not affect 13C levels to a significant extent. Moreover, surface water generally has non-enriched 13C levels. Gases produced by thermogenic processes, on the other hand, undergo no such kinetic preferential metabolysis and therefore are not significantly enriched in 12C. As a result, measurement of 12C levels in methane gas produced from coals can indicate whether the coal is undergoing biogenic or thermogenic coalification.
  • The natural abundance of 12C isotopes is about 98.9% of carbon atoms. The natural abundance of 13C isotope is about 1.1%. In water or an aqueous media, the dissolved inorganic carbon (DIC) consists of carbon dioxide/carbonic acids [CO2+H2CO3], bicarbonate [HCO3 ] and carbonate [CO3 2−]. Therefore, the tracer of interest is δ13CDIC, which is defined as the 13C/12C ratio in the sample divided by the standard 13C/12C ratio, minus one, and typically expressed in parts per thousand by then multiplying the result by one thousand. In coal beds, bacteria ferment acetate (CH3COOH→CH4+CO2) and reduce carbon dioxide (CO2+4H2→CH4+2H2O). As a result, bacterial methanogenesis preferentially removes 12C and the remaining DIC is enriched in 13C.
  • A positive δ13CDIC identifies groundwater in which biogenic production of methane has occurred. The δ13CDIC of groundwater that is not associated with methanogenesis have ratios of negative 5% to negative 20%, whereas water coproduced with coal bed methane has ratios as high as +35%.
  • Therefore, there is a need in the art for methods using δ13C enrichment measurements in coal and shale fluids to indicate practical reservoir characteristics of commercial importance, such as hydrologic constraint in aquifers. There is also a need for sensor devices that can perform such measurements rapidly and effectively in coal bed and shale fluid reservoirs. The present disclosure was made to address this need.
  • SUMMARY
  • The present disclosure provides a method for determining hydrologic constraints in unconventional reservoirs, comprising:
      • (a) determining levels of naturally-occurring 13C in a typical unconventional reservoir;
      • (b) determining the level of 13C in a target unconventional reservoir; and
      • (c) comparing the 13C levels between a typical unconventional reservoir to a target unconventional reservoir to show if there have been changes to hydrologic constraint from one or a plurality of operations in the target unconventional reservoir. For purposes of this disclosure, a typical unconventional coalbed methane reservoir may have ratios of δ13CDIC as high as +35%. A target unconventional reservoir is a coalbed or shale reservoir under investigation using the methods and apparatus of this disclosure.
  • Preferably, the unconventional reservoirs are coal bed reservoirs and shale fluid reservoirs. Preferably, the operations in the target unconventional reservoir are selected from the group consisting of cementing of casing in a wellbore intersecting more than one reservoir, hydraulic fracturing of a reservoir, horizontal drilling in a reservoir, and combinations thereof.
  • The present disclosure further provides a method for determining hydrologic constraints in unconventional reservoirs, comprising:
      • (a) determining levels of naturally-occurring 13C in a typical Unconventional reservoir;
      • (b) determining the level of naturally-occurring 13C in a target unconventional reservoir; and
      • (c) comparing the levels of 13C between the typical unconventional reservoir and the target unconventional reservoir to determine whether the target unconventional reservoir has less reservoir constraints than the typical unconventional reservoir.
  • Preferably, the unconventional reservoirs are coal bed reservoirs or shale fluid reservoirs. Preferably, a difference in respective levels of 13C between the typical and the target reservoirs is used to predict future production success or failure of the target reservoir. Preferably, the levels of 13C are determined by use of Raman spectroscopy. Preferably, the operations in the target unconventional reservoir are selected from the group consisting of cementing of casing in a wellbore intersecting more than one reservoir, hydraulic fracturing of a reservoir, horizontal drilling in a reservoir, and combinations thereof. More preferably, the levels of 13C are compared to the levels of levels of 12C in order to produce a δ13C enrichment level.
  • The present disclosure further provides a method for determining hydrologic constraints in unconventional reservoirs, comprising:
      • (a) determining or obtaining levels of naturally-occurring 13C in a typical unconventional reservoir;
      • (b) determining the level of 13C in a target unconventional reservoir a plurality of times; and
      • (c) comparing the 13C levels between the typical unconventional reservoir to the target unconventional reservoir each time to show if there have been changes to hydrologic constraint from one or a plurality operations in the target unconventional reservoir.
  • The present disclosure also provides a method for determining extent of hydraulic fracturing of a target unconventional reservoir, comprising:
      • (a) determining levels of naturally-occurring 13C in a target unconventional reservoir;
      • (b) hydraulically fracturing the target unconventional reservoir to create a fractured reservoir;
      • (c) determining levels of 13C in the fractured reservoir; and
      • (d) comparing the levels of 13C in the target unconventional reservoir of step (a) to the fractured reservoir of step (c) to evaluate determine if non-reservoir fluids have begun entering the reservoir as a measure of extent of hydraulic fracturing.
  • Preferably, the unconventional reservoirs are coal bed reservoirs or shale fluid reservoirs. Preferably, a difference in respective levels of 13C in the target reservoir before and after fracturing is used to predict future production success or failure of the target reservoir. Preferably, the levels of 13C are determined by use of Raman spectroscopy. Preferably, the levels of 13C are compared to the levels of levels of 12C in order to produce a δ13C enrichment level.
  • BRIEF DESCRIPTION OF THE FIGURES
  • The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate preferred embodiments of the invention. These drawings, together with the general description of the invention given above and the detailed description of the preferred embodiments given below, serve to explain the principles of the invention.
  • FIG. 1 shows representative Raman spectra of the bicarbonate ion containing (A) 12C and (B) 13C atoms dissolved in water.
  • FIG. 2 shows a representative log of δ13C enrichment in naturally occurring bicarbonate ions dissolved in reservoir fluid, as measured downhole using a Raman spectrometer in a coalbed methane well.
  • FIG. 3 shows a representative graph of δ13C enrichment for reservoir fluids produced from a coal seam before and after hydraulic fracturing was completed on the coal seam. The decrease in δ13C enrichment after hydraulic fracturing indicated that the induced fractures connected to one or more adjoining fluid reservoirs, thereby reducing the coal seam's hydraulic constraint, increasing the fluid volumes necessary to be produced in order to produce gas from the coal seam, and injecting hydraulic fracturing fluids and chemicals into the adjoining fluid reservoir or reservoirs.
  • FIG. 4 graphs positive δ13CDIC measurement in produced waters from various coalbed reservoirs, showing particularly highly enriched 13C quantities in fields A and B of 4 fields (A through D).
  • FIG. 5 graphs gas production from 4 fields over 2.5 years.
  • FIG. 6 graphs the water gas ratio of 4 fields (A through D) as a function of δ13CDIC.
  • DETAILED DESCRIPTION
  • Without being bound by theory, the hypothesis underpinning the disclosed method is that coals contain 13C enriched fluids. The level of δ13C enrichment is a characteristic of each zone and field. Moreover, surface and non-coal aquifers do not have 13C enriched aqueous fluids. Therefore, measuring 13C levels confirms if an aqueous fluid comes from a coal bed. Further, any measured decrease in δ13C enrichment from a baseline measurement is thus directly proportional to an influx of aqueous fluid from non-coal zones. As a result, the disclosed method is novel and has not been employed during commercial exploration and production of coal bed methane and shale gas.
  • The present disclosure provides a new reservoir evaluation technology that allows operators to high grade prospective shale and coalbed gas properties and target pay zones, allowing operators to avoid non-economic completion costs and water use. By providing a method and apparatus that can be used to quickly, accurately and inexpensively assess shale and coalbed gas resources at a high data density, this disclosure enables more complete evaluation of shale and coalbed gas resources. This evaluation focuses operators on developing completion methods for shale and coalbed gas targets that warrant investment, reduce overall water usage, and increase the conversion of shale and coalbed gas resources into shale and coalbed gas reserves. The disclosed method removes uncertainty regarding possible fluid influx into reservoirs via recharge or invasion, incenting more rapid capital investment by shale and coalbed gas operators and investors, and accelerating natural gas production from these reservoirs. The disclosed method enables shale and coalbed gas operators to increase exploration success rates, reduce finding costs, reduce completion costs, and reduce environmental impacts without constraining production.
  • Methods for Determining 13C Levels
  • Typical methods for measuring the relative levels of 12C and 13C in fluids produced from coals and shales involve the use of various type of mass spectrometer laboratory instruments. In order to employ such methods, it is necessary to
      • 1. collect fluid samples from a zone of interest, or from wells completed in a zone of interest and producing fluid from that zone;
      • 2. insure that such samples are not affected by subsequent oxidation or other spurious chemical processes or contaminants;
      • 3. transport such samples to a laboratory equipped with appropriate analytical equipment;
      • 4. analyze the samples for 12C and 13C levels; and
      • 5. compare those levels to the levels typical or expected for the zone of interest in order to ascertain hydrological constraint in the zone of interest.
        This ex situ process is tedious, time consuming, costly and limited in nature. Analysis of multiple fluid samples is difficult and therefore evaluation of how fluid properties may vary over time is not facilitated by this method. Therefore, a need exists for a method for measuring the relative levels of 12C and 13C in fluids produced from coals and shales that operates in situ.
  • Disclosed herein is a method of using an optical spectrometer to measure in situ the relative levels of 12C and 13C in fluids produced from coals and shales. This method involves measuring the fundamental vibrational frequencies for molecular bonds and moieties in carbon containing salts. Such vibrational frequencies depend on the weight of the atoms participating in the vibrational moments. Thus, the fundamental vibrational frequencies of 12C containing molecular bonds occur at higher energies than the fundamental vibrational frequencies of 13C containing molecular bonds and moieties.
  • A variety of optical spectroscopies, including but not limited to Raman spectroscopy, infrared spectroscopy, and near-infrared spectroscopy, measure the fundamental vibrational frequencies, or combinations of fundamental vibrational frequencies, in molecules.
  • In Raman spectroscopy, the shift in vibrational frequency between 12C and 13C is approximately proportional to the vibrational shift expected for a spring connecting two masses, where one mass is increased in mass from 12 mass units to 13 mass units. For bicarbonate, the reduction in vibrational frequency for a molecule containing 13C (as compared to a molecule containing 12C) is about 1.8% or about 20 wavenumbers. Representative spectra of both 12C and 13C containing bicarbonate ion dissolved in water are shown in FIG. 1.
  • Therefore, a Raman spectrometer capable of resolving the 12C and 13C peaks, and detecting accurately changes in the relative sizes of those peaks, can be used to measure the relative δ13C enrichment in coal seam and shale gas reservoir fluids.
  • Raman spectroscopy has been successfully adapted for use in coal seam and shale gas wells, as set forth in previously incorporated U.S. Pat. No. 6,678,050 to Pope et al. Therefore, this invention discloses for the first time the use of Raman spectrometers to measure 13C enrichment levels in situ, downhole, in coal seam and shale gas wells.
  • Likewise, Raman spectroscopy has been successfully adapted for use in analyzing at the wellhead fluids produced from coal seam and shale gas reservoirs. See pending application entitled In-Situ Detection And Analysis Of Methane In Coal Bed Methane Formations With Spectrometers, Ser. No. 61/602,939, filed Feb. 24, 2012 which is incorporated in its entirety by reference herein. Therefore, this invention discloses for the first time the use of Raman spectrometers to measure δ13C enrichment levels in situ, at the wellhead, in coal seam and shale gas fluid discharge streams.
  • In a preferred embodiment, a Raman spectrometer suitable for use in a well is obtained using previously disclosed inventions. One such Raman spectrometer is the device used by the assignee, which is an epi-illuminated, grating equipped Raman spectrometer with a 532 nm laser excitation and charge-coupled device (CCD) detector packaged into a 3-inch diameter, 80 inch long high pressure steel housing. The spectrometer interrogates the surrounding gases or fluids via a one-inch sapphire window located at bottom of its housing. The spectrometer communicates to a surface computer and power unit via a standard four-conductor wireline.
  • The Raman spectrometer wireline tool top sub is connected to a cable head that is connected to a four-conductor wireline spool of appropriate length. The spectrometer is powered up by connecting a power supply to two of the four wires in the wireline. The surface computer communicates with and controls the spectrometer via the other two wires.
  • The spectrometer is operated at the wellhead in order to check its operation and calibration. It is then lowered into the well while Raman spectra are collected at 10 second intervals and then transmitted to the surface computer over a subsequent 20 seconds. When the spectrometer encounters reservoir fluid in the wellbore, the Raman spectrum characteristic of that fluid is measured and transmitted to the surface computer. The human operator reviews that spectrum for quality and character to confirm its origin, and the computer processes that spectrum for spectral features of interest, such as position of peaks and number of photons comprising one or more particular peaks.
  • In a well containing 12C and 13C isotopes of particular chemicals, such as dissolved bicarbonate, the Raman spectrometer measures one position and number of photons comprising a 12C-related bicarbonate vibrational mode and a different position and number of photons comprising a peak corresponding to the 13C-related bicarbonate vibrational mode. The human operator and/or the computer then evaluate the positions and number of photons for each peak and relate them to each other and/or to a calibration scale measured under controlled laboratory conditions. In this manner, the amount of δ13C enrichment in a reservoir fluid is quickly and conveniently measured in a wellbore.
  • For example, a five inch diameter steel casing was completed into a twelve-foot thick coal seam by perforation of the casing. The coal seam was located at 890 feet below surface to 902 feet below surface. Perforations were made from 892 feet below surface to 900 feet below surface. The perforations were performed with 50 feet of water cushion above the perforating gun. The coal seam subsequently flowed 340 feet of additional fluid into the wellbore, so that the wellbore contained 390 feet of fluid total above the mean depth of the coal seam. The top of the fluid column was therefore located at 506 feet below surface. A three-inch diameter, 80 inch long wireline Raman spectrometer tool was subsequently lowered into the wellbore while it was continuously collecting Raman spectra. When it encountered fluid in the wellbore, the Raman spectrometer subsequently collected and transmitted Raman spectra of that fluid (primarily water) and of the analytes in that fluid (primarily methane and bicarbonate containing both 12C and 13C isotopes). The spectra were then processed by the computer according to algorithms well known to those skilled in the art of vibrational spectroscopy to produce the concentrations of each bicarbonate isotope at each measured depth. Those concentrations were then mathematically compared to produce a 30% average δ13C enrichment in the dissolved bicarbonate present at each depth in the fluid column, as shown in FIG. 2. The self consistent character of the resulting data at 556 feet below surface reflects the fact that the wellbore contained reservoir fluid at depths greater than 556 feet below surface. This fact was corroborated by examination of the methane concentration and total dissolved solids measured concurrently throughout the fluid column. Based on this result, the coal seam in which that well was completed was judged to be highly constrained. Since the methane gas content measured for the coal seam was of economic quantities, and since the drawdown required to produce gas from the coal seam was measured to be only 145 psia, the coal seam was judged to be an attractive production target.
  • Similar measurements can be undertaken using a variety of fluid handling techniques. For example, the example analysis described above could also be undertaken for multiple coal seams intersected by a cased and cemented wellbore where the casing is perforated sequentially starting with the deepest coal and fluid from each zone is isolated in the casing using an bridge plug, inflation packer, or similar device and Raman spectroscopy testing of δ13C enrichment is subsequently undertaken on each isolated fluid.
  • In a further example, the example analysis described above could also be undertaken for multiple coal seams intersected by a cased and cemented wellbore where the casing is perforated in all zones and then the fluid from each zone is isolated and produced using a drill stem testing string, straddle packer, or similar device and Raman spectroscopy testing of δ13C enrichment is subsequently undertaken on each isolated fluid.
  • In a further example, the example analysis described above could also be undertaken for multiple coal seams intersected by an uncased wellbore where each seam is isolated and fluid from each seam is produced using a drill stem testing string, straddle packer, or similar device and Raman spectroscopy testing of δ13C enrichment is subsequently undertaken on each isolated fluid.
  • In a further example, the example analysis described above could also be undertaken wherein the Raman spectroscopy testing of δ13C enrichment is performed using a Raman spectrometer located at the wellhead that is connected to a fiber optic assembly that is subsequently lowered into the wellbore to contact the fluid. The Raman spectroscopy analysis is then undertaken using the fiber optic assembly to deliver the excitation radiation and collect the scattered photons.
  • In some cases, it may be useful to compare the δ13C enrichment measurements described herein with standard water, gas and coal analysis results in order to describe more comprehensively the coal seam or shale gas reservoir. Such comparison can assist in interpretation of the data sets. The combination of such analyses with the δ13C enrichment measurements described herein is considered a part of the invention disclosed here.
  • Methods of Using Determined 13C Levels
  • This invention discloses for the first time the use of δ13C enrichment data to assess whether drilling and completion operations create new flow channels for fluids between the target coal or shale zone and other zones near a wellbore. In particular, this invention describes a method of testing an untreated coal or shale zone in order to establish its naturally characteristic δ13C enrichment level, treating the coal or shale zone, retesting the coal or shale zone to evaluate whether the treatment created new fluid flow channels to other zones, and then using that information to determine whether the coal or shale zone is an appropriate production target. That information can also be used to determine whether the treatment resulted in contamination to the surrounding zones. That information can also be used to refine the treatment itself in order to reduce or eliminate said contamination.
  • For example, a five inch diameter steel casing was completed into a twelve-foot thick coal seam by perforation of the casing. The coal seam was located at 890 feet below surface to 902 feet below surface. Perforations were made from 892 feet below surface to 900 feet below surface. The perforations were performed with 50 feet of water cushion above the perforating gun. The coal seam subsequently flowed 340 feet of additional fluid into the wellbore, so that the wellbore contained 390 feet of fluid total above the mean depth of the coal seam. The top of the fluid column was therefore located at 506 feet below surface. A three-inch diameter, 80 inch long wireline Raman spectrometer tool was subsequently lowered into the wellbore while it was continuously collecting Raman spectra. When it encountered fluid in the wellbore, the Raman spectrometer subsequently collected and transmitted Raman spectra of that fluid (primarily water) and of the analytes in that fluid (primarily methane and bicarbonate containing both 12C and 13C isotopes). The spectra were then processed by the computer according to algorithms well known to those skilled in the art of vibrational spectroscopy to produce the concentrations of each bicarbonate isotope at each measured depth. Those concentrations were then mathematically compared to produce a 30% average δ13C enrichment in the dissolved bicarbonate present at each depth in the fluid column, as shown in FIG. 2. The self consistent character of the resulting data at 556 feet below surface reflects the fact that the wellbore contained reservoir fluid at depths greater than 556 feet below surface. This fact was corroborated by examination of the methane concentration and total dissolved solids measured concurrently throughout the fluid column. Based on this result, the coal seam in which that well was completed was judged to be highly constrained. Since the methane gas content measured for the coal seam was of economic quantities, and since the drawdown required to produce gas from the coal seam was measured to be only 145 psia, the coal seam was judged to be an attractive production target. Hydraulic fracturing of the coal seam was undertaken in order to increase its effective permeability in order to increase its water and gas flow rates. 30,000 barrels of fluid were injected into the seam at 1,500 psia in order to fracture the seam. Subsequently, fluid was produced back until the solution gas and salinity measured for the fluid became constant, indicating that the frac fluids had all been removed from the formation and the produced fluid was reservoir fluid. Subsequently, fluid was sampled from the water discharge pipe and conveyed to a laboratory where δ13CDIC was measured to be 12% enriched. FIG. 3 shows a graph of the δ13CDIC in fluids collected from the coal seam before and after hydraulic fracturing. Because the post-frac fluid δ13CDIC was reduced substantially from the pre-frac δ13CDIC level, it was concluded that the hydraulic fracturing process fractured through the coal seam and into an overlaying limestone.
  • One group of Atlantic Rim springs have positive δ13CDIC. Enriched Lewis shale springs have Na-HCO3-type water, and some of them emit methane. Enriched Lewis shale springs have higher total dissolved contents (TDS) of 800-4000 mg/L than springs with negative δ13CDIC (TDS typically 1064 <1000 mg/L). These springs occur together in clusters up dip of the coal bed natural gas (CBNG) production areas. The variations in abundance of methane emerging from these springs may be related to local variations in hydrostatic pressure of the near-surface methane-bearing reservoirs or influx from other gas-saturated coal bed reservoirs. Although water produced with CBNG are Na-HCO3-type water with relatively high TDS (>1000 mg/L) and positive δ13CDIC. Water samples from wells with low water/gas ratios have the highest δ13CDIC and produce the most gas. Water samples from wells with lower, although still positive, δ13CDIC values reflect the addition of isotopically light water from other reservoirs. Structure contour mapping identifies faults in proximity to low δ13CDIC wells. Geochemical analysis of δ13CDIC help to identify CBNG and shale natural gas reservoirs with the highest potential for natural gas production while minimizing unnecessary water production.
  • The present disclosure predicts a correlation between water/gas ratios, production potential, efficiency, and δ13CDIC. δ13CDIC should be less enriched in coal bed reservoirs that are hydraulically connected to multiple water sources with isotopically light carbon compositions. An unconfined coal bed reservoir is likely to produce more water during CBNG production than a confined coal bed reservoir, as the hydraulic pressure of multiple connected reservoirs would need to be reduced to promote CBNG desorption. A group of wells in a single coal bed, which have highly enriched δ13CDIC values and low cumulative water/gas ratios, appear to be producing from confined coal bed reservoirs. Another group of wells, which are not as enriched regarding δ13CDIC and have high cumulative water/gas ratios, are likely producing from partially confined or unconfined coal bed reservoirs. δ13CDIC may help producers determine in which geographic areas coal bed reservoir water has undergone the most biologic methanogenic activity and/or those coal bed reservoirs that are confined.
  • Enrichment of δ13CDIC is directly related to bacterial methanogenesis. The generation of thermogenic gas will not enrich DIC ratios, and δ13CDIC characterization is inapplicable in CBNG reservoirs that are exclusively thermogenic. The δ13CDIC alone cannot identify which specific isotopically light reservoirs are in communication with coal bed reservoirs. Water quality, well log, and geologic interpretation of likely reservoirs may aid in distinguishing these reservoirs.
  • A δ13CDIC measurement can characterize CBNG reservoirs. Moreover, carbon isotopic tracers in produced water can guide CBNG development to those areas where natural gas production is maximized and water production is minimized. Positive δ13CDIC of CBNG produced water indicates that bacterial methanogenesis is associated with these waters (FIG. 4). However, a significant range in δ13CDIC exists in Field A CBNG samples, which provides additional information about the potential for CBNG production from individual wells and related reservoirs (FIG. 5).
  • Analyte concentrations also increase with distance from faults. These measurements can determine if CBNG reservoirs and shale bed natural gas (SBNG) reservoirs in a particular area are partially confined or unconfined as a result of faulting. This is because water with isotopically light carbon compositions and lesser amounts of brine to mix into the coal bed reservoir.
  • δ13CDIC measurements can analyze CBNG production potential, particularly in hydraulically confined CBNG reservoirs. This capability alone makes δ13CDIC a significant coal bed reservoir and CBNG analysis tool (FIG. 6). A correlation is predicted between water/gas ratios, production potential, efficiency, and δ13CDIC, as: (a) δ13CDIC should be less enriched in coal bed reservoirs that are hydraulically connected to multiple water sources with isotopically light carbon compositions. (b) An unconfined coal bed reservoir is likely to produce more water during CBNG production than a confined coal bed reservoir, as the hydraulic pressure of multiple connected reservoirs would need to be reduced to promote CBNG desorption.
  • Enrichment of δ13CDIC is directly related to bacterial methanogenesis. The generation of thermogenic gas will not enrich DIC ratios, and δ13CDIC characterization is inapplicable in CBNG reservoirs that are exclusively thermogenic. δ13CDIC alone cannot identify which specific isotopically light reservoirs are in communication with coal bed reservoirs. Water quality, strontium isotopic compositions, well log, and geologic interpretation of likely reservoirs may aid in distinguishing these reservoirs. δ13CDIC analysis records the characteristics of the produced water at the time the wells were sampled.
  • The foregoing disclosure has been set forth merely to illustrate the invention and is not intended to be limiting. Since modifications of the disclosed embodiments incorporating the spirit and substance of the invention may occur to persons skilled in the art, the invention should be construed to include everything within the scope of the appended claims and equivalents thereof.
  • This specification is to be construed as illustrative only and is for the purpose of teaching those skilled in the art the manner of carrying out the invention. It is to be understood that the forms of the invention herein shown and described are to be taken as the presently preferred embodiments. As already stated, various changes may be made in the shape, size and arrangement of components or adjustments made in the steps of the method without departing from the scope of this invention. For example, equivalent elements may be substituted for those illustrated and described herein and certain features of the invention maybe utilized independently of the use of other features, all as would be apparent to one skilled in the art after having the benefit of this description of the invention.
  • While specific embodiments have been illustrated and described, numerous modifications are possible without departing from the spirit of the invention, and the scope of protection is only limited by the scope of the accompanying claims.

Claims (25)

We claim:
1. A method for determining hydrologic constraints in unconventional reservoirs, comprising:
a. determining levels of naturally-occurring 12C and 13C isotopes in a typical unconventional reservoir using a Raman spectroscopy instrument placed downhole and in communication with a computer for data analysis;
b. determining the level of naturally-occurring 12C and 13C isotopes in a target unconventional reservoir using the Raman spectroscopy instrument placed downhole and in communication with the computer for data analysis;
c. comparing the levels of 12C and 13C between the typical unconventional reservoir and the target unconventional reservoir, and
d. the computer calculating concentrations of 12C and 13C isotopes at each measured depth.
2. The method of claim 1 wherein the analyte subject of Raman spectroscopy comprises DIC containing both 12C and 13C isotopes.
3. The method of claim 1 wherein the Raman spectrometer comprises a high pressure steel tube with a diameter less than 5 inches, a sapphire window at a bottom end of the housing to irradiate samples and a laser excitation source and a charge-coupled device detector.
4. The method of claim 3 wherein the Raman spectrometer is continuously collecting Raman spectra.
5. The method of claim 3 wherein the Raman spectrometer collects Raman spectra at least once every 60 seconds.
6. The method for determining hydrologic constraints in unconditional reservoirs of claim 1 further comprising comparing the levels of 12C and 13C isotopes between the typical unconventional reservoir and the target reservoir to determine whether the target unconventional reservoir has less reservoir constraints than the typical unconventional reservoir.
7. The method for determining hydrologic constraints in unconventional reservoirs of claim 1, wherein the unconventional reservoirs are coal bed reservoirs or shale fluid reservoirs.
8. The method for determining hydrologic constraints in unconventional reservoirs of claim 1, further comprising using a difference in respective levels of 12C and 13C isotopes between the typical unconventional reservoir and the target reservoirs to predict gas production levels of the target reservoir.
9. The method for determining hydrologic constraints in unconventional reservoirs of claim 1, wherein the levels of 12C and 13C isotopes are determined by use of Raman spectroscopy.
10. The method for determining hydrologic constraints in unconventional reservoirs of claim 1, wherein operation in the target unconventional reservoir comprises cementing of casing in a wellbore intersecting more than one reservoir, hydraulic fracturing of a reservoir, or horizontal drilling in a reservoir.
11. The method for determining hydrologic constraints in unconventional reservoirs of claim 10, wherein the levels of 13C are compared to the levels of levels of 12C in order to produce a 13C enrichment level.
12. A method for determining hydrologic constraints in unconventional reservoirs, comprising:
a. obtaining levels of naturally-occurring 12C and 13C in a typical unconventional reservoir;
b. obtaining the level of 12C and 13C in a target unconventional reservoir a plurality of times; and
c. comparing the 12C and 13C levels between the typical unconventional reservoir to the target unconventional reservoir each time to show if there have been changes to hydrologic constraint from one or a plurality of operations in the target unconventional reservoir.
13. A method for determining hydrologic constraints in unconventional reservoirs of claim 12 further wherein the changes in hydrologic constraint comprise cementing of casing in a wellbore intersecting more than one reservoir, hydraulic fracturing of a reservoir or horizontal drilling in a reservoir.
14. The method for determining hydrologic constraints in unconventional reservoirs of claim 12, wherein the unconventional reservoirs are coal bed reservoirs or shale fluid reservoirs.
15. A method for determining extent of hydraulic fracturing of a target unconventional reservoir using Ramen spectroscopy and computer analysis, comprising:
a. interrogating fluid samples with Ramen spectroscopy in a target unconventional reservoir;
b. communicating spectra data to a computer;
c. determining levels of naturally-occurring 12C and 13C isotopes in the target unconventional reservoir;
d. hydraulically fracturing the target unconventional reservoir to create a fractured reservoir;
e. interrogating fluid samples with Ramen spectroscopy in a fractured target unconventional reservoir;
f. communicating spectra data to a computer;
g. determining levels of 12C and 13C isotopes in the fractured target unconventional reservoir; and
h. comparing ratios of 12C and 13C isotopes in the target unconventional reservoir of step (c) to the fractured target unconventional reservoir of step (g) to evaluate if non-reservoir fluids have begun entering the fractured target unconventional reservoir as a measure of extent of hydraulic fracturing.
16. The method for determining the extent of hydraulic fracturing of the fractured target unconventional reservoir of claim 15, wherein the targeted unconventional reservoirs are coal bed reservoirs or shale fluid reservoirs.
17. The method for determining the extent of hydraulic fracturing of a fractured target unconventional reservoir of claim 15, wherein a difference in respective relative levels of 13C in the target unconventional reservoir before and after fracturing is used to predict future production success or failure of the target unconventional reservoir.
18. The method for determining the extent of hydraulic fracturing of a target unconventional reservoir of claim 15, wherein the levels of 13C are compared to the levels of 12C in order to produce a δ13C enrichment level.
19. An apparatus to measure in situ levels of 12C and 13C in fluids produced from coals and shales wherein the apparatus is a Raman spectrometer.
20. The apparatus of claim 19 further comprising a high pressure steel housing.
21. The apparatus of claim 20 further comprising an epi-illuminated, Raman spectrometer with a laser excitation and charge-coupled device detector.
22. The apparatus of claim 20 further comprising a sapphire window in the housing to illuminate the sample.
23. A method of determining the of δ13C enrichment in reservoir fluids comprising the steps of:
a) lowering a spectrometer into a well bore on a wireline;
b) encountering reservoir fluids;
c) collecting Raman spectra of an illuminated fluid sample at 60 second intervals or less;
d) transmitting the spectra to a computer; and
e) evaluating positions and number of photons for each peak of spectra and relating the peaks to each other or to a calibration scale.
25. A method of predicting gas production potential from a coalbed formation comprising
a) calculating δ13CDIC;
b) calculating cumulative water/gas ratios over time;
c) correlating production potential and efficiency with δ13CDIC and water/gas ratios.
26. A method of using δ13CDIC to evaluate geographic areas of coalbed reservoir water having biologic methanogenic activity.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111815196A (en) * 2020-07-23 2020-10-23 中国环境科学研究院 Method for evaluating water resource bearing capacity of shale GAs development area based on GA-BP neural network
CN117074241A (en) * 2023-10-13 2023-11-17 太原理工大学 Method for measuring content of water participating in spontaneous combustion reaction product of coal based on isotope tracking

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105134185B (en) * 2015-08-12 2017-12-05 中国石油天然气股份有限公司 Properties of fluid in bearing stratum recognition methods
WO2017197346A1 (en) * 2016-05-13 2017-11-16 Gas Sensing Technology Corp. Gross mineralogy and petrology using raman spectroscopy
CN108614294A (en) * 2018-04-17 2018-10-02 中国石油天然气股份有限公司 A kind of trap Screening Treatment method and device
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US11047233B2 (en) 2019-08-28 2021-06-29 Saudi Arabian Oil Company Identifying hydrocarbon sweet spots using carbon dioxide geochemistry
CN113030430B (en) * 2021-03-17 2023-02-17 中煤科工集团重庆研究院有限公司 Method for measuring and calculating concentration of free coal bed gas in reservoir of mining stable area of coal mine
CN115165847A (en) * 2022-07-07 2022-10-11 中煤科工集团上海有限公司 Coal rock spectrum sensing device and coal mining machine comprising same

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5684580A (en) * 1995-05-01 1997-11-04 Ashland Inc. Hydrocarbon analysis and control by raman spectroscopy
US6018389A (en) * 1996-07-22 2000-01-25 The Regents Of The University Of California Cone penetrometer fiber optic raman spectroscopy probe assembly
US20030048450A1 (en) * 2000-04-11 2003-03-13 Welldog, Inc. In-situ detection and analysis of methane in coal bed methane formations with spectrometers
US20030053049A1 (en) * 2001-09-04 2003-03-20 Fink Manfred F. Detecting isotopes and determining isotope ratios using raman spectroscopy
US20050007583A1 (en) * 2003-05-06 2005-01-13 Baker Hughes Incorporated Method and apparatus for a tunable diode laser spectrometer for analysis of hydrocarbon samples
US20060240572A1 (en) * 2004-08-24 2006-10-26 Carron Keith T System and method for Raman spectroscopy assay using paramagnetic particles
US20080111064A1 (en) * 2006-11-10 2008-05-15 Schlumberger Technology Corporation Downhole measurement of substances in earth formations
US20090288881A1 (en) * 2008-05-22 2009-11-26 Schlumberger Technology Corporation Methods and apparatus to form a well
US20100089142A1 (en) * 2007-01-03 2010-04-15 Council Of Scientific & Industrial Research process utilizing natural carbon-13 isotope for identification of early breakthrough of injection water in oil wells
US20100228485A1 (en) * 2009-03-09 2010-09-09 Soraya Betancourt Method for integrating reservoir charge modeling and downhole fluid analysis
US20100224365A1 (en) * 2009-03-06 2010-09-09 Carlos Abad Method of treating a subterranean formation and forming treatment fluids using chemo-mathematical models and process control
US20100326651A1 (en) * 2009-06-30 2010-12-30 Bp Corporation North America Inc. Isotopic identification of production by individual formations in commingled gas wells
US20110017458A1 (en) * 2009-07-24 2011-01-27 Halliburton Energy Services, Inc. Method for Inducing Fracture Complexity in Hydraulically Fractured Horizontal Well Completions
US7933718B2 (en) * 2006-08-09 2011-04-26 Momentive Specialty Chemicals Inc. Method and tool for determination of fracture geometry in subterranean formations based on in-situ neutron activation analysis
US20110297370A1 (en) * 2010-06-07 2011-12-08 Conocophillips Company Hydrocarbon production allocation methods and systems
US20120036923A1 (en) * 2009-04-23 2012-02-16 The Regents Of The University Of California Tracer method to estimate rates of methane generation through augmentation or biostimulation of the sub-surface

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3239666A (en) 1962-10-17 1966-03-08 Pan American Petroleum Corp Production of hydrocarbons from multizone wells

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5684580A (en) * 1995-05-01 1997-11-04 Ashland Inc. Hydrocarbon analysis and control by raman spectroscopy
US6018389A (en) * 1996-07-22 2000-01-25 The Regents Of The University Of California Cone penetrometer fiber optic raman spectroscopy probe assembly
US20030048450A1 (en) * 2000-04-11 2003-03-13 Welldog, Inc. In-situ detection and analysis of methane in coal bed methane formations with spectrometers
US20030053049A1 (en) * 2001-09-04 2003-03-20 Fink Manfred F. Detecting isotopes and determining isotope ratios using raman spectroscopy
US20050007583A1 (en) * 2003-05-06 2005-01-13 Baker Hughes Incorporated Method and apparatus for a tunable diode laser spectrometer for analysis of hydrocarbon samples
US20060240572A1 (en) * 2004-08-24 2006-10-26 Carron Keith T System and method for Raman spectroscopy assay using paramagnetic particles
US7933718B2 (en) * 2006-08-09 2011-04-26 Momentive Specialty Chemicals Inc. Method and tool for determination of fracture geometry in subterranean formations based on in-situ neutron activation analysis
US20080111064A1 (en) * 2006-11-10 2008-05-15 Schlumberger Technology Corporation Downhole measurement of substances in earth formations
US20100089142A1 (en) * 2007-01-03 2010-04-15 Council Of Scientific & Industrial Research process utilizing natural carbon-13 isotope for identification of early breakthrough of injection water in oil wells
US20090288881A1 (en) * 2008-05-22 2009-11-26 Schlumberger Technology Corporation Methods and apparatus to form a well
US20100224365A1 (en) * 2009-03-06 2010-09-09 Carlos Abad Method of treating a subterranean formation and forming treatment fluids using chemo-mathematical models and process control
US20100228485A1 (en) * 2009-03-09 2010-09-09 Soraya Betancourt Method for integrating reservoir charge modeling and downhole fluid analysis
US20120036923A1 (en) * 2009-04-23 2012-02-16 The Regents Of The University Of California Tracer method to estimate rates of methane generation through augmentation or biostimulation of the sub-surface
US20100326651A1 (en) * 2009-06-30 2010-12-30 Bp Corporation North America Inc. Isotopic identification of production by individual formations in commingled gas wells
US20110017458A1 (en) * 2009-07-24 2011-01-27 Halliburton Energy Services, Inc. Method for Inducing Fracture Complexity in Hydraulically Fractured Horizontal Well Completions
US20110297370A1 (en) * 2010-06-07 2011-12-08 Conocophillips Company Hydrocarbon production allocation methods and systems

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111815196A (en) * 2020-07-23 2020-10-23 中国环境科学研究院 Method for evaluating water resource bearing capacity of shale GAs development area based on GA-BP neural network
CN117074241A (en) * 2023-10-13 2023-11-17 太原理工大学 Method for measuring content of water participating in spontaneous combustion reaction product of coal based on isotope tracking

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